Synthesis and Characterization of Semiconductive Dichloridobis(thianthrene)gold(1+) Tetrachloridoaurate(1–)

Abstract

AbstractA new (thianthrene)gold(III) complex has been synthesized in liquid SO2 as the solvent from thianthrene (TA) andAuCl3. [AuCl2(TA)2][AuCl4] [triclinic, P$\bar {1}$, a = 9.9832(2) Å, b = 10.3404(2) Å, c = 15.0798(4) Å, α = 75.038(1)°, β = 81.610(1)°, γ = 68.409(1)°, V = 1396.15(5) Å3, Z = 2] has a salt‐like structure consisting of [AuCl2(TA)2]+ and [AuCl4]– ions, both with square‐planar coordinated gold atoms of oxidation state +3. In the cation, two bent TA molecules are coordinated to Au each through one sulfur atom. The title compound is thermally stable up to 425 K and is semiconducting with a conductivity reaching 25 mSm–1 at 380 K and a low activation energy of 0.43 eV. A model for the charge transport along the stacked cationic complexes is discussed. When dissolved in chloroform [AuCl2(TA)2][AuCl4] is converted into the already known uncharged, mononuclear complex [AuCl3(TA)], which shows that a polymerization isomerism exists between the two forms.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)